EP0463740B1 - Schutzschichten - Google Patents

Schutzschichten Download PDF

Info

Publication number
EP0463740B1
EP0463740B1 EP91304855A EP91304855A EP0463740B1 EP 0463740 B1 EP0463740 B1 EP 0463740B1 EP 91304855 A EP91304855 A EP 91304855A EP 91304855 A EP91304855 A EP 91304855A EP 0463740 B1 EP0463740 B1 EP 0463740B1
Authority
EP
European Patent Office
Prior art keywords
barrier
lamellae
atomic oxygen
formaldehyde
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91304855A
Other languages
English (en)
French (fr)
Other versions
EP0463740A1 (de
Inventor
John Allan Barnes
William James Brennan
William Neville Eugon Meredith
Florence Huguette Gilberte Cowan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Publication of EP0463740A1 publication Critical patent/EP0463740A1/de
Application granted granted Critical
Publication of EP0463740B1 publication Critical patent/EP0463740B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264Up to 3 mils
    • Y10T428/2651 mil or less
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/31859Next to an aldehyde or ketone condensation product
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/31859Next to an aldehyde or ketone condensation product
    • Y10T428/31862Melamine-aldehyde
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/31909Next to second addition polymer from unsaturated monomers
    • Y10T428/31924Including polyene monomers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/31931Polyene monomer-containing
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31942Of aldehyde or ketone condensation product

Definitions

  • the invention relates to protective barriers and to components protected thereby.
  • the present invention relates to, and is concerned with, the use of layer minerals which exhibit barrier properties against atomic oxygen.
  • an aerospace vehicle comprises external surfaces susceptible to atomic oxygen attack which have a protective barrier against such attack, said barrier comprising a substantially continuous layer of lamellae of a film-forming, 2:1 phyllosilicate layer mineral which exhibit barrier properties against atomic oxygen.
  • an aerospace vehicle component comprises external surfaces susceptible to atomic oxygen attack which have a protective barrier against such attack, said barrier comprising a substantially continuous layer of lamellae of a film-forming, 2:1 phyllosilicate layer mineral which exhibits barrier properties against atomic oxygen.
  • the invention is directed to the use as a protective barrier against atomic oxygen attack of lamellae of a film-forming, 2:1 phyllosilicate layer mineral which exhibit barrier properties against atomic oxygen.
  • lamellae as used in this specification means tiny particles of the layer mineral obtained by subjecting the mineral to a chemical delaminating process to form an aqueous colloidal dispersion of high aspect ratio particles or platelets of the mineral from which a film can be formed.
  • the lamellae have a thickness of less than 0.5»m, usually less than 0.05»m and preferably of the order of or less than 0.005»m and an aspect ratio (ie length or breadth divided by thickness) of at least 10, preferably at least 100 and up to 1000 or more, eg 10000.
  • the layer mineral is selected from the group consisting of smectites, preferably hectorite and montmorillonite, and vermiculite.
  • vermiculite as used in this specification means all materials known mineralogically and commercially as vermiculite including chlorite-vermiculites.
  • barriers having surprising and significant protective barrier properties against atomic oxygen comprise a substantially continuous layer of lamellae at very low thicknesses, eg as low as 0.025»m, but preferably the minimum thickness of the layer is at least 0.1»m, preferably at least 0.3»m, and particularly up to 1»m.
  • the layer mineral is vermiculite.
  • the barrier preferably comprises, particularly when the layer mineral is vermiculite, at least one component selected from a binder and a polymeric anchor coating interposable between the lamellae and the substrate or surface.
  • the binder is an organic binder and may be any film-forming polymeric or oligomeric species or precursor therefor that assists in forming a film of the lamellae of the layer mineral and does not disrupt the film-forming capability thereof.
  • the polymeric binder is selected from functionalised polyolefins, especially maleimised polybutadiene, and a liquid formaldehyde resin such as urea formaldehyde, melamine formaldehyde, phenol formaldehyde, resorcinol formaldehyde, cresol formaldehyde or mixtures thereof, especially melamine formaldehyde.
  • the binder when present, comprises at least 5% by weight of the layer and, more particularly, between 10% and 50%, and especially between 15% and 35%, by weight of the layer.
  • the polymeric anchor coating comprises a styrene/acrylamide copolymer of the type more particularly described in GB-A-1174328 and GB-A-1134876.
  • the anchor coating when present, is less than 1»m thick and, more particularly, is less than 0.5»m, especially less than 0.25»m, thick.
  • the protective barrier is formed by applying the lamellae as a slurry or dispersion and removing the dispersion medium to form a coherent layer.
  • the dispersion medium comprises water and the slurry or dispersion comprises between 0.5% and 20%, more especially between 1% and 10%, by weight of lamellae.
  • the substrate to which the protective barrier is applied in accordance with the invention is conveniently selected from structural parts of aerospace vehicles which have surfaces which are exposed to atomic oxygen environments in use or to components thereof exposed to those environments in use, the components being for example solar panels (the barriers being relatively flexible and transparent over a wide range of electromagnetic frequencies) and antennae.
  • the substrate may also be a polymeric film.
  • the polymeric film is selected from aromatic polyesters and aromatic polymers comprising divalent aromatic units containing divalent connecting groups selected from ketone, sulphone, sulphoxide or imide, the units being connected by ether and/or thioether linkages.
  • a free-standing film of vermiculite lamellae was prepared by forming a wet film of lamellae of vermiculite slurry GP-903 available from W R Grace & Co and allowing the film to dry in air.
  • the wet film was formed on a glass substrate using a 2% by weight aqueous slurry of the lamellae.
  • the resultant film was 30»m thick.
  • Samples of the film were subjected to a simulated atomic oxygen regime using a research plasma reactor available from Polar Materials Inc, USA, the samples being located on a 127mm diameter powered aluminium electrode spaced 44.5mm from a 114mm copper electrode. Parts of the samples were masked using a small silicon wafer on the surface of the sample to enable etch depths to be analysed using an ⁇ -step analyser available from Tencor, USA.
  • vermiculite lamellae film samples exhibited a weight loss following removal from the reactor after treatment, allowing the samples to equilibrate in ambient atmosphere caused the sample weights to return to the untreated values. Furthermore, using the ⁇ -step analyser, no measurable step could be discerned on the material surface. Scanning electron micrographs of the untreated and treated samples showed no discernible differences.
  • vermiculite lamellae film appeared to be unaffected by the simulated atomic oxygen environment to which it had been subjected.
  • the polymers show little resistance to the simulated atomic oxygen environment.
  • Samples of a polymer composite of Victrex PEEK and carbon fibres available from ICI under the trade name APC-2 were subjected to the simulated atomic oxygen environment described in Example 1 following degassing for 1 hour.
  • the samples tested were approximately 3mm thick and had a surface area of about 10 ⁇ 3m ⁇ 2.
  • the samples were coated with lamellae of vermiculite slurry GP-903, available from W R Grace & Co, USA (using a 6.5% by weight slurry which included about 20% by weight of maleinised polybutadiene as a binder), and a synthetic hectorite available from Laporte Industries Limited under the trade name Laponite B (using a 2% by weight slurry).
  • the 0.3»m vermiculite coating was achieved using a number 2 Meyer bar and the Laponite B and the thicker vermiculite coatings were achieved using a number 4 Meyer bar.
  • virgin APC-2 composite material and APC-2 composite material having an aluminium coating deposited thereon by electron beam evaporation were also subjected to the simulated atomic oxygen environment described in Example 1. The results are summarised in Table 2.
  • Samples of APC-2 were coated with lamellae of vermiculite and Laponite B slurries as described in Example 3. Meyer bars numbers 2 and 4 were used for the vermiculite and the Laponite B, respectively.
  • the slurry contained 6.5% by weight of the lamellae and varying amounts of the polymeric binders maleimised polybutadiene (MPBD) or melamine formaldehyde resin (MF).
  • One sample (marked * in Table 3 below) was pre-coated with a polymeric anchor coat of a styrene/ 2-ethyl hexyl acrylate/methacrylic acid/N-butoxymethyl acrylamide copolymer of the type described in the aforementioned GB-A-1174328 and GB-A-1134876.
  • the coating was applied using a number 1 Meyer bar as a 3% by weight solution in isopropyl alcohol and containing sulphuric acid as catalyst and dried in air at ambient temperature to give a dry coating of thickness 0.12»m.
  • the coated samples were then subjected to an adhesion test.
  • the samples were cross-scored on their coated side to give a plurality of rectangles of substantially equal area.
  • An adhesive tape was then applied to the scored coating and the area of coating remaining adhered to the substrate was determined and is quoted as a percentage in Table 3 below.
  • a sample was made similar to that marked * in Table 3 above and it was subjected to thermal cycling from liquid nitrogen temperature to 90°C. The adhesion of the vermiculite coating to the APC-2 substrate appeared to improve.
  • samples of ICI development composites designated APC (HTA) (the polymeric matrix being a polyethersulphone and APC (ITX) (the polymeric matrix being a polyetherketone).
  • HTA the polymeric matrix being a polyethersulphone
  • APC the polymeric matrix being a polyetherketone
  • the samples were coated with lamellae of vermiculite slurries GP-903 using a 6.5% by weight slurry which included about 20% by weight of MPBD as binder and with Laponite B using a 2% by weight slurry.
  • the 0.3»m vermiculite coating was achieved using a number 2 Meyer bar and the Laponite B and the thicker vermiculite coatings were achieved using a number 4 Meyer bar.
  • Table 4 The results are summarised in Table 4.
  • Example 6 The procedure of Example 6 was repeated for further samples and the coatings and results are summarised in Table 5. The samples were equilibriated for 14 days before the mass loss figures were determined. Vermiculite slurry GP-923 is also available from W R Grace & Co. Sumecton (trade name) is a synthetic hectorite available from Kunimine Industries, Japan.
  • a 1-2»m layer of Laponite S lamellae was formed on a silica substrate and the absorbance of radiation in the visible and UV regions was determined for it.
  • the sample had a low absorbance, ie it was substantially transparent to the radiation, in both the visible and UV regions.
  • Subtrates precoated with an anchor coat as described in Example 4, were coated with bentonite which was applied as 7.5% by weight aqueoue slurry which included 35% by weight of MF as binder using Meyer bars numbers 2 and 6 to achieve dry coating thicknesses of 0.3»m and 1.7»m, respectively. Both samples were degassed for 1 hour and subjected to the simulated atomic oxygen environment described in Example 1. Even without equilibriation, both samples exhibited good barrier properties, ie ⁇ 100»g/cm2 weight loss.
  • Polymeric films were assessed in the reactor as described in Example 1 both without a protective coating and with a protective coating, the films assessed being:-
  • the samples were mounted in a ring having an inwardly-extending flange which protected the periphery of the film.
  • the samples were degassed for 1 hour and the quoted mass losses of the samples were determined after a 5 day equilibrium period.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Road Signs Or Road Markings (AREA)

Claims (15)

  1. Raumfahrtfahrzeug, das äußere Oberflächen umfaßt, die anfällig gegen einen atomaren Sauerstoffangriff sind, das eine Schutzbarriere gegen einen derartigen Angriff hat, wobei diese Barriere eine im wesentliche kontinuierliche Schicht von Lamellen eines filmbildenden, 2:1 Phyllosilicatschichtmineral ist, das Barriere-Eigenschaften gegen atomaren Sauerstoff zeigt.
  2. Raumfahrtfahrzeugkomponente, das äußere Oberflächen umfaßt, die anfällig gegen einen atomaren Sauerstoffangriff sind, das eine Schutzbarriere gegen einen derartigen Angriff hat, wobei diese Schicht eine im wesentliche kontinuierliche Schicht von Lamellen eines filmbildenden, 2:1 Phyllosilicatschichtminerals ist, das Barriere-Eigenschaften gegen atomaren Sauerstoff zeigt.
  3. Verwendung der Lamellen eines filmbildenden, 2:1 Pyllosilicatschichtminerals, das Barriere-Eigenschaften gegen atomaren Sauerstoff zeigt als Schutzbarriere gegen einen Angriff atomaren Sauerstoffs.
  4. In der Erfindung, wie in jedem der vorangehenden Ansprüche definiert, umfaßt diese Barriere zumindest eine Komponente, die aus einem polmeren Bindemittel und einer polymeren Haftschicht ausgewählt wird, die zwischen die Lamellen und das Substrat oder die Oberfläche dazwischen angeordnet werden kannn.
  5. In der Erfindung, wie in Anspruch 4 definiert, umfaßt das polymere Bindemittel ein funktionalisiertes Polyolefin, insbesondere maleimisiertes Polybutadien und ein flüssiges Formaldehydharz, wie Harnstofformaldehyd, Melaminformaldehyd, Phenolformaldehyd, Resorcinformaldehyd, Kresolformaldehyd oder Mischungen davon, insbesondere Melaminformaldehyd.
  6. Schutzbarriere auf einem Substrat zum Schutz der Oberfläche darauf gegen einen atomaren Sauerstoffangriff, wobei diese Barriere eine im wesentlich kontinuierliche Schicht von Lamellen eines filmbildenden, 2:1 Phyllosilicatschichtminerals ist, das Barriere-Eigenschaften gegen atomaren Sauerstoff in einem polymeren Bindemittel zeigt, wobei dieses Bindemittel ein funktionalisiertes Polyolefin, insbesondere maleimisiertes Polybutadien und ein flüssiges Formaldehydharz, wie Harnstofformaldehyd, Melaminformaldehyd, Phenolformaldehyd, Resorcinformaldehyd, Kresolformaldehyd oder Mischungen davon, insbesondere Melaminformaldehyd umfaßt.
  7. In der Erfindung, wie in jedem einzelnen der Ansprüche 4 bis 6 definiert, umfaßt das Bindemittel, falls vorhanden, zumindest 5 Gew.% der Schicht und bevorzugter zwischen 10 Gew.% und 30 Gew.% und insbesondere zwischen 15 Gew.% und 25 Gew.% der Schicht.
  8. Schutzbarriere auf einem Substrat zum Schutz einer Oberfläche darauf gegen atomaren Sauerstoffangriff, wobei diese Barriere eine im wesentliche kontinuierliche Schicht von Lamellen eines filmbildenden, 2:1 Phyllosilicatschichtminerals, das Barriere-Eigenschaften gegen atomaren Sauerstoff zeigt und eine polymere Haftschicht, die zwischen die Barriere und dieses Substrat dazwischen angeordnet werden kann, umfaßt.
  9. In der Erfindung, wie in jedem einzelnen der Ansprüche 4 bis 8 definiert, umfaßt die polymere Haftschicht, falls vorhanden, ein Styrol/Acrylamid Copolymer und besonders bevorzugt ein Styrol/2-Ethylhexylacrylat/Methacrylsäure/N-Butoxymethylacrylamid Copolymer.
  10. In der Erfindung, wie in jedem einzelnen der Ansprüche 4 bis 9 definiert, ist die Haftschicht, falls vorhanden, weniger als 1 »m dick und besonders bevorzugt weniger als 0,5 »m, insbesondere weniger als 0,25 »m dick.
  11. In der Erfindung, wie in jedem einzelnen der vorangehenden Ansprüchen definiert, wird das Schichtmineral aus der Gruppe, die aus Smectiten, bevorzugt Hectorit und Montmorillonit und Vermiculit besteht, ausgewählt.
  12. In der Erfindung, wie in jedem einzelnen der vorangehenden Ansprüchen definiert, umfaßt diese Barriere im wesentlichen eine kontinuierliche Schicht von Lamellen von zumindestens 0,1 »m, bevorzugt zumindest 0,3 »m dick und insbesondere bis zu 1 »m dick.
  13. In der Erfindung, wie in jedem einzelnen der vorangehenden Ansprüche definiert, ist das Schichtmineral Vermiculit.
  14. In der Erfindung, wie in jedem einzelnen der vorangehenden Ansprüche definiert, wird die Schutzbarriere gebildet, indem die Lamellen als wäßrige Aufschlämmung oder Dispersion aufgebracht werden und das Wasser entfernt wird, um eine kohärente Schicht zu bilden.
  15. In der Erfindung, wie in Anspruch 14 definiert, enthält die Aufschlämmung oder Dispersion zwischen 0,5% und 20%, besonders bevorzugt zwischen 1% und 10% des Gewichts an Lamellen.
EP91304855A 1990-06-20 1991-05-29 Schutzschichten Expired - Lifetime EP0463740B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9013702 1990-06-20
GB909013702A GB9013702D0 (en) 1990-06-20 1990-06-20 Protective barriers

Publications (2)

Publication Number Publication Date
EP0463740A1 EP0463740A1 (de) 1992-01-02
EP0463740B1 true EP0463740B1 (de) 1995-12-06

Family

ID=10677883

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91304855A Expired - Lifetime EP0463740B1 (de) 1990-06-20 1991-05-29 Schutzschichten

Country Status (7)

Country Link
US (1) US5234761A (de)
EP (1) EP0463740B1 (de)
JP (1) JP2997093B2 (de)
CA (1) CA2044218A1 (de)
DE (1) DE69115136T2 (de)
ES (1) ES2080250T3 (de)
GB (1) GB9013702D0 (de)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9102374D0 (en) * 1991-02-04 1991-03-20 Ici Plc Polymeric film
GB9112827D0 (en) * 1991-06-14 1991-07-31 Ici Plc Polymeric film
GB9112843D0 (en) * 1991-06-14 1991-07-31 Ici Plc Polymeric film
US5312685A (en) * 1992-07-06 1994-05-17 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Atomic oxygen protective coating with resistance to undercutting at defect sites
US6361876B1 (en) * 1992-08-10 2002-03-26 Mcdonnell Douglas Corporation Durable protected optical coatings
EP0627495B1 (de) * 1993-05-10 1998-08-12 Optical Coating Laboratory, Inc. Selbstheilende UV-undurchlässige Beschichtung mit flexiblem Polymersubstrat
EP0666612B1 (de) * 1994-02-04 2001-10-24 Orbital Sciences Corporation Sich selbst entfaltende Wendelstruktur
US5668565A (en) * 1994-12-22 1997-09-16 Orbital Science Corporation Flexible feed line for an antenna system
US6087016A (en) * 1997-06-09 2000-07-11 Inmat, Llc Barrier coating of an elastomer and a dispersed layered filler in a liquid carrier
US6232389B1 (en) 1997-06-09 2001-05-15 Inmat, Llc Barrier coating of an elastomer and a dispersed layered filler in a liquid carrier and coated articles
AU7837198A (en) * 1997-06-09 1998-12-30 Herberts G.M.B.H. Aqueous coating composition of a polymer and exfoliated platelet filler
US7303797B1 (en) * 1999-02-16 2007-12-04 E.I. Du Pont De Nemours And Company Gas barrier coating system for polymeric films and rigid containers
CN105151324A (zh) * 2015-09-22 2015-12-16 上海卫星工程研究所 天基成像雷达卫星原子氧遮蔽装置及其使用方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5320959B2 (de) * 1973-05-14 1978-06-29
US4174358A (en) * 1975-05-23 1979-11-13 E. I. Du Pont De Nemours And Company Tough thermoplastic nylon compositions
EP0044160B1 (de) * 1980-07-11 1986-09-17 Imperial Chemical Industries Plc Faserige Verbundstoffe sowie deren Herstellung und Verwendung
EP0075396B1 (de) * 1981-09-14 1985-06-05 Imperial Chemical Industries Plc Wässrige Überzugsmittel
US4664980A (en) * 1984-09-14 1987-05-12 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Oxidation protection coatings for polymers
US4800041A (en) * 1985-11-04 1989-01-24 Armstrong World Industries, Inc. Suspensions of sheet silicate materials and products made therefrom
US4980206A (en) * 1986-09-15 1990-12-25 The Boeing Company Method for improving atomic oxygen resistance
DE3707388A1 (de) * 1987-03-07 1988-09-15 Basf Lacke & Farben Waessrige schichtsilikatdispersionen, verwendung dieser dispersionen als lackhilfsmittel und wasserverduennbare, schichtsilikate enthaltende beschichtungszusammensetzungen
DE3823967A1 (de) * 1988-07-15 1990-01-18 Heinz B Mader Plattenfoermiges, ebenes oder gewoelbtes bauelement in sandwichbauweise, insbesondere zur verwendung in luftfahrzeugen

Also Published As

Publication number Publication date
JP2997093B2 (ja) 2000-01-11
ES2080250T3 (es) 1996-02-01
EP0463740A1 (de) 1992-01-02
DE69115136D1 (de) 1996-01-18
JPH04250035A (ja) 1992-09-04
US5234761A (en) 1993-08-10
DE69115136T2 (de) 1996-06-05
GB9013702D0 (en) 1990-08-08
CA2044218A1 (en) 1991-12-21

Similar Documents

Publication Publication Date Title
EP0463740B1 (de) Schutzschichten
Schmidt et al. Epoxy adhesion to metals
US5780163A (en) Multilayer coating for microelectronic devices
KR100745852B1 (ko) 미세균열 저항성이 개선된 적층 제품 및 그의 제조방법
US5609925A (en) Curing hydrogen silsesquioxane resin with an electron beam
EP0659904B1 (de) Verdampftes Hydrogensilsesquioxan zum Anscheiden eines Überzugs
EP0900250B2 (de) Schutzbeschichtungen aus lithium- und kaliumkopolysilikates
US5753374A (en) Protective electronic coating
AU2003284639A1 (en) Gas barrier multilayer film
EP1373388B1 (de) Trennfilme
US4791008A (en) Coating compositions and method for improving the properties of coated substrates
Kayhan et al. Evaluation of two new white silicone thermal control paints under atomic oxygen
US5629066A (en) Resin article having anti-static property
Marinkovic et al. Preparation and properties of sputtered “glassy” carbon films
US6004680A (en) Method of coating pre-primed polyolefin films
Konstadinidis et al. X-ray photoelectron study of chemical interactions at Ti/polymer interfaces
Yoshiaki et al. Wettability control of polystyrene by ion implantation
US5569493A (en) Preparation of cured cyanate ester resins and composites for metal plating
EP0832945B1 (de) Zusammensetzung für Überzugsmittel und Verbundfilm
Pola et al. Polymer-stabilized nano-sized tellurium films by laser-induced chemical vapour co-deposition process
Watanabe Aluminium nitride thin films prepared by ion beam assisted deposition method
Jeong et al. Reaction mechanism between BN‐sprayed graphite and molten Al in vacuum, and its application to the evaporation source for reactive metals including Al
Nakamae et al. Characterization of the interface between a cured epoxy resin and aluminum
Ruckman et al. Ion and electron beam processing of condensed molecular solids to form thin films
Shi et al. Ion-beam induced modifications of Sb Al bilayers

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE ES FR GB IT

17P Request for examination filed

Effective date: 19920527

17Q First examination report despatched

Effective date: 19931001

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE ES FR GB IT

REF Corresponds to:

Ref document number: 69115136

Country of ref document: DE

Date of ref document: 19960118

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2080250

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed
ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20020508

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20020522

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20020529

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20020610

Year of fee payment: 12

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030529

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030530

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031202

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20030529

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040130

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20030530

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050529